Proof of thermodynamic stability condition

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Discussion Overview

The discussion revolves around a mathematical detail in the proof of the thermodynamic stability condition as presented in Kardar's Statistical Mechanics course. Participants explore the relationships between intensive and extensive variables in a homogeneous system at equilibrium, particularly focusing on the implications of dividing the system into two subsystems that can exchange energy.

Discussion Character

  • Technical explanation
  • Conceptual clarification
  • Debate/contested

Main Points Raised

  • One participant seeks clarification on the statement that intensive variables are functions of extensive coordinates, specifically how variations in energy, volume, and particle number affect temperature, current density, and chemical potential.
  • Another participant provides a mathematical perspective, suggesting that if temperature is a function of energy, then variations in energy lead to corresponding variations in temperature for the subsystems.
  • A subsequent reply questions the assumption that the intensive variables remain equal between the two subsystems, arguing that the derivatives of the function relating temperature to energy may differ if the subsystems are not identical.
  • Another participant acknowledges the earlier point and agrees that since the overall system is at equilibrium, the intensive variables must indeed be the same for both subsystems.

Areas of Agreement / Disagreement

Participants express differing views on the equality of intensive variables between the subsystems, with some arguing that they can differ due to the nature of the subsystems, while others assert that equilibrium implies equality.

Contextual Notes

The discussion highlights the complexity of the relationships between intensive and extensive variables and the assumptions made regarding equilibrium in thermodynamic systems. There is an acknowledgment of the dense nature of the material being discussed.

chimay
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Question about a mathematical detail in the proof of the thermodynamic stability relation
I am watching Kardar's Statistical Mechanics course in my spare time and I am struggling to understand a mathematical detail in the proof of the thermodynamic stability condition. See Eq. I.62 here.

The author considers a homogeneous system at equilibrium with intensive and extensive variables (T,J,\mu) and (E,x,N), respectively. Then, He imagines that the latter system is divided into two subsystems (A and B) that can exhange energy. Under the assumption that E,x and N are conserved, we have \delta E_A=-\delta E_B, \delta x_A=-\delta x_B and \delta N_A=-\delta N_B. What is not clear to me is the statement "Since the intensive variables are themselves functions of the extensive coordinates, to first order in the variations of (E, x, N), we have \delta T_A=-\delta T_B, \delta J_A=-\delta J_B and \delta \mu_A=-\delta \mu_B."

Can anyone explain to me the previous statement more in detail?

Thank you!
 
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If, for example, ##T=f(E)##, then to the first order, ##\delta T=f'\, \delta E##.
Then, ##\delta E_A = -\delta E_B## implies ##\delta T_A = -\delta T_B##.
 
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Hi Hill, thank you for your reply.
I understand your point:
\delta T_A = \frac{\partial f}{\partial E}\bigg\rvert_{T_A} \delta E_A and
\delta T_B = \frac{\partial f}{\partial E}\bigg\rvert_{T_B} \delta E_B.

However, since the two subsystems are not necessarily equal, even though \delta E_A = - \delta E_B, \delta T_A \ne \delta T_B because \frac{\partial f}{\partial E}\bigg\rvert_{T_A} \ne \frac{\partial f}{\partial E}\bigg\rvert_{T_B}.

Where am I wrong?
 
chimay said:
However, since the two subsystems are not necessarily equal, even though δEA=−δEB, δTA≠δTB because ∂f∂E|TA≠∂f∂E|TB.
They say, "The two subsystems, A and B, initially have the same values for the intensive variables". That is, ##T_A=T_B##. Then, ##\frac{\partial f}{\partial E}\bigg\rvert_{T_A} = \frac{\partial f}{\partial E}\bigg\rvert_{T_B}##.
 
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You are right! I read it so many times but I missed that. Indeed, since the overall system is at equilibrium, it makes sense that the two "subsystems" have the same values for the intensive variables. Kardar's book is very dense of information and I find it hard to follow sometimes...

Thank you for your help!
 
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